Ruthenium dihydrogen complex for C-H activation

Catalytic H/D exchange under mild conditions

Martin H G Prechtl, Markus Hölscher, Yehoshoa Ben-David, Nils Theyssen, David Milstein, Walter Leitner

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.

Original languageEnglish
Pages (from-to)3493-3500
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number22
DOIs
Publication statusPublished - Aug 2008

Fingerprint

Ruthenium
Ion exchange
Activation energy
Chemical activation
Regioselectivity
Catalysts
Alkenes
Benzene
Discrete Fourier transforms
Protons
Carbon
Nuclear magnetic resonance
Kinetics
Substrates
naphthalene

Keywords

  • CH activation
  • Deuteration
  • DFT calculations
  • H/D exchange
  • Ruthenium dihydrogen complexes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ruthenium dihydrogen complex for C-H activation : Catalytic H/D exchange under mild conditions. / Prechtl, Martin H G; Hölscher, Markus; Ben-David, Yehoshoa; Theyssen, Nils; Milstein, David; Leitner, Walter.

In: European Journal of Inorganic Chemistry, No. 22, 08.2008, p. 3493-3500.

Research output: Contribution to journalArticle

Prechtl, Martin H G ; Hölscher, Markus ; Ben-David, Yehoshoa ; Theyssen, Nils ; Milstein, David ; Leitner, Walter. / Ruthenium dihydrogen complex for C-H activation : Catalytic H/D exchange under mild conditions. In: European Journal of Inorganic Chemistry. 2008 ; No. 22. pp. 3493-3500.
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